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High concentrations of organic contaminants in air from ship breaking activities in Chittagong, Bangladesh Therese Haugdahl Nøst, Anne Karine Halse, Scott Randall, Anders Borgen, Martin Schlabach, Alak Paul, Atiqur Rahman, and Knut Breivik Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.5b03073 • Publication Date (Web): 09 Sep 2015 Downloaded from http://pubs.acs.org on September 15, 2015

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Environmental Science & Technology

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High concentrations of organic contaminants in air from ship breaking

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activities in Chittagong, Bangladesh

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Therese H. Nøst1*, Anne K. Halse2, Scott Randall2,3, Anders R. Borgen2, Martin Schlabach2,

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Alak Paul4, Atiqur Rahman4,5 and Knut Breivik2,6

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1

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Tromsø, Norway;

NILU-Norwegian Institute for Air Research, FRAM Centre, P.O. Box 6606 Langnes, 9296

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2

NILU-Norwegian Institute for Air Research, P.O. Box 100, 2027 Kjeller, Norway;

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3

COWI AS, Division of Environment, Economics and Planning, P.O. Box 123, 1601

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Fredrikstad, Norway;

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4

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Chittagong, Bangladesh;

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5

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& Atmospheric Environment, 210044 Nanjing, China;

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6

University of Chittagong, Department of Geography and Environmental Studies, 4331

Nanjing University of Information Science and Technology, School of Atmospheric Physics

University of Oslo, Department of Chemistry, P.O. Box 1033, 0315 Oslo, Norway.

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*Corresponding author: phone: (+47) 77 75 03 86; fax: (+47) 77 75 03 76; [email protected].

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Abstract

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The beaches on the coast of Chittagong in Bangladesh are one of the most intense ship

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breaking areas in the world. The aim of the study was to measure the concentrations of

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organic contaminants in the air in the city of Chittagong, including the surrounding ship

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breaking areas using passive air samplers (N=25). The compounds detected in the highest

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amounts were the polycyclic aromatic hydrocarbons (PAHs) and short-chain chlorinated

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paraffins (SCCPs), whereas dichlorodiphenyltrichloroethanes (DDTs), hexachlorobenzene

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(HCB) and polychlorinated biphenyls (PCBs) were several orders of magnitude lower in

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comparison. PCBs, PAHs and HCB were highest at sites near the ship breaking activities,

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whereas DDTs and SCCPs were higher in the urban areas. Ship breaking activities likely act

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as atmospheric emission sources of PCBs, PAHs and HCB thus adding to the international

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emphasis on responsible recycling of ships. Concentrations of PAHs, PCBs, DDTs, HCB and

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SCCPs in ambient air in Chittagong are high in comparison to similar studies performed in

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other parts of Asia. Estimated toxic equivalent quotients (TEQs) indicate elevated human

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health risks caused by inhalation of PAHs at most sites.


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Introduction

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Environmental impacts of hazardous anthropogenic substances is a global concern which has

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motivated international regulatory initiatives such as the Stockholm1 and Basel Conventions2.

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Persistent organic pollutants (POPs) and their potential harmful effects to humans and the

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environment have been researched extensively in industrialized countries, but far less is

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known about POPs emission sources and environmental concentrations in developing

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countries. Bangladesh is classified as a Least Developed Country according to the United

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Nations (UN). In addition, Bangladesh has ratified the Stockholm and the Basel Conventions.

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Since the 1980's, national environmental regulations have existed in Bangladesh such as the

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banning of many organochlorine pesticides and polychlorinated biphenyls (PCBs).3 There are

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several suspected local emission sources of POPs in Bangladesh;3-5 however, there are few

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studies monitoring concentrations of POPs in the environment in this country, and no studies

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have been conducted in Chittagong.

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Chittagong is the second largest city in Bangladesh and has a population of approximately 4.5

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million people.6 The city hosts a large seaport and extensive industrial activities in and around

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the city. Ship breaking in Chittagong occurs when ships are dismantled directly on the tidal

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beaches. This activity began in the 1960's and has since represented a considerable share of

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the world market of ship breaking.5, 7-10 Out of a total of 1026 ships dismantled globally in

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2014, 22% of the ships with known scrapping destinations were dismantled in the Chittagong

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area.11 Concern has arisen regarding these activities and the subsequent emissions of

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pollutants to the environment.12-14 The materials making up the scrapped ships contain heavy

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metals and industrial-use POPs like PCBs and polybrominated diphenyl ethers (PBDEs).15 A

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large fraction of the volume of waste electric and electronic equipment (WEEE) in

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Bangladesh originates from the ship breaking activities.5, 16 Furthermore, there is no formal

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management and recycling of obsolete PCB-containing equipment, and this waste is simply 3 ACS Paragon Plus Environment


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deposited in landfills in many areas.3, 5 Burning of such waste could release POPs like PCBs

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to the air while also generating by-products of combustion such as polycyclic aromatic

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hydrocarbons (PAHs).17, 18

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Other potential sources to contaminants in the ambient air in Chittagong area include release

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and/or generation of unintentionally produced PCBs and PAHs by industrial activities.17-20

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Also, there are suspected stockpiles and illegal use of pesticides in the area, especially of

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dichlorodiphenyltrichloroethane (DDT) - which was produced in Chittagong until 1991.3, 4

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Metal-working lubricants, sealants, plasticizers, and flame retardants are likely widely used in

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Bangladesh, which may contain short-chain chlorinated paraffins (SCCPs) which can also be

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considered a pollutant source.21

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There is limited information on the environmental and human exposure to POPs as a result of

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ship breaking activities. The objective of this study was to monitor concentrations of PCBs,

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organochlorine pesticides, PBDEs, SCCPs and PAHs in the air within the urban environment

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of Chittagong, including a focus on areas with ship breaking activities.

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Materials and methods

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Sample collection

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The sampling campaign was conducted in the Chittagong area using passive air samplers

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(PAS) equipped with polyurethane foam (PUF) disks.22 PAS are regularly used for spatial

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mapping of pollutants in air monitoring studies on both a regional and global scale.23-27.

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Detailed descriptions of this sampling method can be found in literature.22, 25, 26, 28 In brief, the

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PUF disk has a high ability to sorb semi-volatile organic compounds in air and thus

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accumulate such compounds on the disk during the exposure period. The theoretical amount

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sorbed on the PUF disk is equivalent to the rate of uptake minus the rate of loss. The initial

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rate of uptake is linear, but declines as the concentration in the PUF approaches equilibrium.

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The duration of the linear phase of uptake is dependent on the octanol– air partition

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coefficient (KOA) of the individual compounds. Thus, compounds that are more volatile (low

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KOA) will approach equilibrium faster than less volatile compounds (higher KOA).

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A total of 25 PAS were deployed at 23 different sites in Chittagong and near the ship

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breaking areas located northwest of the city center in late February 2013 (Supporting

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Information (SI), Figure S1). The study was performed in parallel to a screening study for

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concentrations of sulphur dioxide (SO2), nitrogen dioxide (NO2), and ozone (O3) in ambient

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air of Chittagong.29 Deployment time for the PAS ranged from 7 to 9 days, see SI, Table S1

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for details. A short deployment time was deliberately selected (i) because high frequencies of

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detection were anticipated for most analytes, and (ii) to enhance the potential for sampling

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during the linear uptake phase, reflecting the high temperatures expected during the sampling

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period in combination with the volatility of the target compounds. The samplers were

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assembled, deployed, and disassembled by trained personnel from Chittagong University. The



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sampling campaign also included preparation of field and transport blanks (N=4 and 4,

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respectively).

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The research team selected sampling sites in residential, industrial, and background areas as

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well as in areas in close proximity to ship breaking activities in Chittagong. After the

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exposure period in the field, the samplers were disassembled and the PUF disks were wrapped

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in two layers of aluminum foil, placed in sealed plastic bags, and stored in a freezer until

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analysis.

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The screening study was performed during the dry season and there was no precipitation

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recorded during the sampling period. Temperatures during the sampling period were

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consistently high; 25-30°C high during the day and around 15°C during nighttime. The wind

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frequency distribution (wind rose) as measured at the Agrabad continuous air monitoring

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station in Chittagong is presented for the sampling period in SI, Figure S2. The prevailing

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wind direction in this area was from west-northwest (Bay of Bengal) with wind speeds

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between 1 and 4 m/s.

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Sample preparation, clean-up and analysis

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Sample preparation, clean-up and analysis were performed as described in detail by Halse et

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al.27; only a brief summary along with minor adjustments is provided here. The PUF disks

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were pre-cleaned using Soxhlet extraction (toluene for 24 hours, acetone for 8 hours, and

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toluene for additional 8 hours) before deployment. The disks were wrapped in two layers of

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aluminum foil, placed in sealed plastic bags, and stored in a freezer until shipment. After the

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exposure period, PUF disks were spiked with internal standards and Soxhlet extracted using

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n-hexane/10% diethyl ether (8-10 hours, 250 mL). An aliquot (10% volume of extracts) was


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stored for possible future analysis. The remaining extracts were divided into two identical

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aliquots for two separate clean-up procedures.

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One aliquot targeted acid-resistant compounds: PCBs (congeners 28, 52, 101, 118, 138, 153,

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180), PBDEs (congeners 47, 99), hexachlorocyclohexanes (α-, β- and γ-HCH),

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dichlorodiphenyltrichloroethanes and one metabolite (DDTs; p,p´-DDT, o,p´-DDT, p,p´-

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DDE), hexachlorobenzene (HCB), chlordanes (trans-chlordane, cis-chlordane, trans-

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nonachlor) and SCCPs. This aliquot was treated with concentrated sulfuric acid (2 mL, 2-3

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times) and further cleaned up using a silica column of activated silica (4 g, preheated 8 hours

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at 550 °C) and eluted with n-hexane/10 % diethyl ether (30 mL). The other aliquot targeted

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PAHs (fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene,

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chrysene/triphenylene, benzo(a)pyrene). As PAHs are acid-labile and difficult to elute from

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activated silica, a slightly different clean-up method was applied. The solvent was exchanged

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to cyclohexane before clean up using a deactivated silica column (slurry of 5 g silica

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deactivated with 8% MilliQ water, and 15 mL cyclohexane) and eluted with cyclohexane (100

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mL). After clean-up procedures, the extract aliquots were reduced to ~50 µl and added

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recovery standards.

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The analyses of PCBs, PBDEs, HCHs, DDTs, and HCB were performed by gas

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chromatography coupled to a high resolution mass spectrometer (GC-HRMS) in electron

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impact mode.27 SCCPs and chlordanes were determined by GC-HRMS in an electron capture

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negative ionization mode and reported as bulk mixture.30 PAHs were analyzed by gas

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chromatography coupled to a low resolution mass spectrometer (GC-LRMS) in electron

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impact ionization mode.27

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Quality assurance and quality control

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The analytical procedures were performed according to NS/EN ISO/IEC 17025 accredited

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routines. A calibration/quantification solution containing all target analytes was analysed

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along with the samples. Also, analysis of standard reference materials (SRM 1588 and 2206a,

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National Institute of Standards and Technology) assured low analytical uncertainties of PCBs,

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PBDEs, HCHs, DDTs, HCB and chlordanes. Further, compounds with a retention time of

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more than 3 seconds later than corresponding isotope-labeled standards as well as compounds

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with isomer isotopic ratios deviating >20% from those in the standards were disregarded.

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Average recoveries for internal standards ranged 48-113% and their ranges for the samples

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and blanks are presented in SI, Table S2.

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Field (N=4), transport (N=4) and laboratory method (N=3blanks were extracted and analyzed

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along with samples to reveal any contamination during handling, transport and laboratory

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preparations. Field blanks are defined as PUFs that have been assembled in PAS and then

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immediately disassembled in the field; transport blanks are PUFs which were never exposed

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in the field; and laboratory method blanks are simply clean PUFs. The ranges of blank

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amounts are presented in SI, Table S3. Method detection limits (MDLs) were determined for

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each compound from average blank amounts plus three times the standard deviation of these

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amounts. When the target compound was not identified in the blanks, an instrumental

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detection limit (signal/noise 3:1) was used to estimate a MDL value.

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Parallel samplers were deployed at two sampling sites. Between parallels, the relative

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standard deviations were 0.1-27% for PCBs, 7.8-21% for PBDEs, 2.6-28% PAHs, 3-39% for

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HCHs, 4-34 for p,p’-DDT, 4-28% for HCB, 6% for SCCPs, 0-4% for chlordanes. The average

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value of the parallel samples represented sample results at these sites.


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Estimation of concentrations in air

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A sampling volume estimate is needed to calculate concentrations in air from the measured

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amounts of POPs in the PAS. Still, the most appropriate approach for back-calculation of

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concentrations in air from PAS sampling is currently debated and sample volume estimations

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do include uncertainties.31-34 In the current study, a range for the estimated sampling volume

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was obtained for each compound as proposed by Harner et al.35 The estimation is based on

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duration of exposure, average air temperature, PUF characteristics, compound-specific KOA-

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values and assumptions of sampling rates and particle fractions (see further details in the SI,

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Table S5).

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Data treatment and analysis

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All 23 sites were included in the data analysis. Statistical analysis was executed using R,

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ver.3.1.1., and statistical significance was defined as p < 0.05. When summed amounts were

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calculated for POP groups, MDL/√2 was used for sample amounts that were lower than the

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MDL. Summary statistics for compounds with detection frequencies between 20% and 80%

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were calculated using the Kaplan-Meier method with the NADA package for R according to

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Helsel (2005). Correlations between components are presented as Spearman`s rank

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correlations. Spatial presentation of the data was performed with the ggplot2 and ggmap

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packages in R, in which the background maps are provided by Google Inc. Due to

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uncertainties in back-calculated concentrations in air, spatial patterns are interpreted on the

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basis of measured amounts. Principal component analyses (PCA) were performed with the

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ggbiplot package in R on the compounds presented in SI, Table S3 (SCCPs were excluded

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due to missing values).



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Estimations of human health risks from inhalation exposure

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Toxic equivalent quotients (TEQs) were calculated based on toxic equivalency factors (TEFs)

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for PAHs36 (fluorene=0.001, phenanthrene=0.001, anthracene=0.01, fluoranthene=0.001,

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pyrene=0.001, benz(a)anthracene=0.1, chrysene/triphenylene=0.01, benzo(a)pyrene=1) and

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PCBs37 (PCB-118=0.000033), as well as the PUF-derived concentrations in air for each site.


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Results and discussion

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Results summary

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The measured amounts were highest for PAHs and SCCPs whereas PCBs, DDTs, chlordanes,

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HCB and PBDEs were several orders of magnitude lower in comparison. The correlations

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between compounds within each of the PAH and PCB groups were strong (most Spearman`s

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rho >0.8), whereas correlations were weaker, or not significant, for PBDEs and pesticides (SI,

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Table S4).

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The levels for Σ7PCBs were highest at three sampling sites located close to ship breaking

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activities and especially at one site where measured amounts were 19 times higher than the

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median of Σ7PCBs (Figure 1B). Still, the amounts of Σ7PCBs at the other sampling sites were

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also considerable (Figure 1A). The lower-chlorinated PCB congeners contributed most to the

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Σ7PCBs (34%, 27%, and 15% of Σ7PCBs for PCB-28, -52, -101, respectively; SI, Table S3).

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The levels of PBDEs were low and results are only presented for PBDE-47 and -99 due to

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quality control measures and limitations of the sampling method. The highest amounts of the

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two PBDE congeners were found at sites in the city center.

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The sites with the highest levels of Σ8PAHs (Figure 1C) paralleled those of the PCBs and

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there was moderate correlation of many PAHs with PCBs (Spearman`s rho>0.3; SI, Table

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S4). Phenanthrene (46%), fluoranthene (18%), fluorene (17%), pyrene (14%) contributed

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most to the median Σ8PAHs.

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The highest measured amounts of HCB was found at one site in the vicinity of ship breaking

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activities (Figure 1D) which was same site that had the extreme values for Σ7PCBs and

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Σ8PAHs. However, HCB levels were high also at other sites in the ship breaking area and in

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the city.



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The most abundant pesticides found in the study were DDT and DDE. The highest levels of

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p,p’-DDT (Figure 1E) and o,p’-DDT (data not shown) were found at sites in urban areas. The

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spatial trends for HCHs diverged between the three isomers measured (SI, Figure S3). Levels

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of α-HCH were highest at the urban sites, whereas β-HCH levels were highest at one site near

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ship breaking activities as well as at numerous urban sites. Levels of γ-HCH were highest at

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sites close to ship breaking activities. Sample amounts of chlordanes were low and spatial

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patterns (presented for trans-chlordane in SI, Figure S3) resembled those for γ-HCH.

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The highest levels of SCCPs were found in the urban area (Figure 1F) and there appeared to

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be a declining trend of these levels with increasing distance from the city center. SCCP results

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for the site closest to ship breaking activities that was highest for PCBs and PAHs was

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unfortunately not available as this sample was damaged during laboratory analyses.

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Interpretation of PAH molecular ratios

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Molecular diagnostic ratios (MDRs) are ratios between certain PAHs which can indicate

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characteristics related to their emission sources.38-40 Sampling performed in narrow time spans

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across limited geographical areas close to suspected sources has been suggested to facilitate

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interpretation of MDRs and renders the present study interesting in this context. Three MDRs

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were calculated based on PAHs with high analytical detection (Figure 2). The ratios of

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anthracene/anthracene + phenanthrene (ANT/(ANT + PHE)) and

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benz(a)anthracene/benz(a)anthracene + chrysene (BaA/(BaA + CHR)) were significantly

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different between site classifications (5 classes, see SI, Table S1; Kruskal-Wallis test, p=0.004

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for both group tests). It should be noted that quantified amounts of chrysene include

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uncertainties due to analytical co-elution with triphenylene. The third MDR representing


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fluoranthene/fluoranthene + pyrene (FLT/(FLT + PYR)) was not significantly different across

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classes (Kruskal-Wallis test, p>0.05).

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MDR values above given cut off values indicate combustion of grass and wood rather than

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fossil fuel as sources to PAHs.39, 40 Ratios were above the respective cut off values at four

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sites for ANT/(ANT + PHE) and at six sites for BaA/(BaA + CHR) in the ship breaking area.

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In addition, ratios were above the respective cut off values at three sites for BaA/(BaA +

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CHR) that were classified as industrial or affected by traffic within the city. Together, MDR

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values were high at sites near ship breaking activities and at some industrial sites which

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suggest that PAHs originate from combustion processes at these sites. The FLT/(FLT + PYR)

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ratio was above the cut off value at all sites which could be indicative of widespread

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combustion of wood and grass, etc. Compared to coastal, urban and agricultural sites in

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Southern India, ratio values for BaA/(BaA + CHR) were higher at the sites close to ship

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breaking activities in Chittagong and FLT/(FLT + PYR) values were in the same range.41

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Methodological limitations

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PUF-based PAS was selected as sampling material based on their performance in spatial

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mapping on both a regional and global scale (see references in method section). However,

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employing PUF-based PAS as sampling method of relatively volatile substances has both

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advantages and draw-backs.32 In order to focus the discussion and avoid artifacts due to

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choice of sampling method, the presented results have been limited to compounds in a

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selected range of KOA-values (SI, Table S3; ranging 6.21 - 11.38 at 24°C which was the

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average estimated temperature for the sampling period). An additional limitation is that the

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sampling could be influenced by high amounts of ambient particles as well as the fact that

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there was no precipitation to settle the particles during the sampling period.29 In addition to 13 ACS Paragon Plus Environment


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particle impaction, the high temperatures found during the sampling period may have

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enhanced the uptake of both the gas phase and the particle bound phase of POPs during

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deployment.22 There is likely some variation in particular concentrations and temperatures

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within the study area that might have affected the contaminant uptake at some sampling sites,

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but the spatial comparisons are still considered valid. Overall, the sampling period provides a

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temporal snap shot in the area both with regards to seasonal variability related to changing

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intensities of ship breaking and industrial activities. There was no apparent trend with height

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of sampler position above sea level.

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PUF-derived concentrations in air are presented even though they include uncertainties as

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exact normalization to measured sampling volumes was not possible. Therefore, a range of

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sampling volumes was estimated for each compound based on ranges in temperatures and

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theoretical ranges in ambient particle-fractions during the sampling according to Harner et

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al.35 As the sampling rates vary by uptake phases, gas-particle partitioning, wind speed and

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temperature,32 the estimates may appear crude, however, we have employed a compound-

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specific strategy to take account of the KOA-specific variation in sampling volumes.

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Local emission sources of POPs

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This study presents ambient air data across an area that covers residential, industrial and ship

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breaking areas as well as sites that can be considered background sites. Poor air quality is an

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identified problem in several areas of Bangladesh, also in Chittagong.29, 42, 43 However, to the

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extent of our knowledge no previous survey of POP concentrations in ambient air has been

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performed in Bangladesh. The results of the present study demonstrate high measured

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amounts of various POPs considering the short sampling period. Furthermore, the

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discrepancies in spatial patterns for PCBs, HCB, and PAHs as compared to DDTs and HCHs 14 ACS Paragon Plus Environment

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indicate different emission sources for the different compound classes. Specifically, the

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results indicate that ship breaking activities can be important potential local emission sources

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of PCBs, PAHs and HCB. Furthermore, sites in urban areas appeared to be especially

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influenced by sources of DDTs and SCCPs. Together, these results add to the emphasis on

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challenges related to atmospheric pollution in Chittagong.

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The PCA analyses demonstrated that the main variation in the sample set is related to the

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samples collected close to ship breaking activities and that the other site classes (industrial,

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traffic-influenced, residential, background) are distinguished from these samples (SI, Figure

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S4). Overall, the PAHs, PCBs and HCB were clustered together along the first factor away

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from o,p’-DDT and α-HCH which agrees with the spatial trends of these compounds

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(displayed in Figures 1 and S3). The joint interpretation of spatial patterns in concentration

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trends, PAH MDRs, compound correlations and PCA patterns has provided indications of

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potential emission sources for the different contaminants. Overall, our results are in

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accordance with previously suggested potential emission sources such as release and/or

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production of contaminants related to ship breaking and industrial activities, as well as

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influence of stockpiles of pesticides or PCBs.4

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Ship breaking activities

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The levels of PCBs, PAHs and HCB were high at sites close to the beach and the spatial

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trends for these compounds indicate the role of ship structures and their dismantling processes

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as potential local emission sources of these compounds. Many registered activities in this area

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are designated as iron and steel manufacture, re-rolling mills, and simply as ship breaking.

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The spatial trends for PCBs, PAHs and HCB and their inter-correlations indicate common

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emissions of these compounds which could be related to release and/or formation through

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combustion processes as burning of scrap materials is common in the ship breaking areas.12



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This is further supported by the high MDR ratios indicative of combustion of wood and

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grass42 at sampling sites classified as influenced by ship breaking. Ships may contain PCBs in

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WEEE (e.g. transformers and capacitors) and paints.3, 15 Furthermore, PCBs, PAHs and HCB

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could be generated and/or released during combustion through burning of scrap and organic

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materials from the ships.17-19 The elevated levels of the same POPs at urban sites could also be

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related to ship breaking activities as there is subsequent processing and treatment of materials

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from the ships in Chittagong city.12, 29 Based on prevailing winds, the urban areas are

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downwind from the ship breaking sites and transport by air can also havecontributed to the

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sample amounts at sampling sites in the urban areas.

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-

Industrial sites

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The sampling campaign was conducted in the dry season which is when the most intense

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emission sources are active in Bangladesh. The sources include industrial activities, brick

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kilns, wood burning, metal smelters, road dust, motor vehicles, soil dust, and sea salt – which

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have all been identified as important sources to particulate pollution.29, 42, 43 As the sampling

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campaign was conducted during a period in which industrial activity and particle fractions in

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the air was generally high,29 the sample amounts of PAHs, PCBs and HCB may also reflect

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sampling of target analytes sorbed onto particles.32 A study describing a sampling campaign

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conducted in parallel to the present study has reported concentrations of NO2 and SO2 in

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ambient air. Their spatial distributions were largely in accordance with recognized industrial

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activities and traffic, respectively, but did not display high concentrations at sites near ship

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breaking activities.29 Spatial patterns within the urban areas for POP concentrations that could

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be related to industrial activities crudely correspond with those of NO2 and SO2

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concentrations; this only adds support to the interpretation of the industrial activities as

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contributing emission sources to PAHs, PCBs and HCB in ambient air in the city.

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Accordingly, contributions from various industrial activities have been shown to contribute to 16 ACS Paragon Plus Environment

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the ambient air loading of PCBs20 and could contribute to the spatial patterns of PCBs in

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urban air in Chittagong (Figure 1A).

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Waste sites

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Burning of waste at waste dump sites is common in Bangladesh3 and these combustion

346

processes can release PAHs, PCBs and HCB.18, 19 There are waste sites in the urban areas

347

which also could be contributing to the high measurements at urban sample sites (Figure 1A-

348

D). As mentioned, further processing of materials from ships could result in waste in urban

349

areas3, 29 thereby also contribute to emissions to ambient air at those sites.

350

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Stockpiles and use of pesticides

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The spatial trends for DDTs indicated emission sources in urban areas which could be

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explained by historic production of DDT in the Chittagong area as well as stockpiles and

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continued illegal use.3, 4 The median p,p’-DDT/ p,p’-DDE ratio was 1.92 (ranging 0.87 –

354

2.82) and the median o,p’-DDT/ p,p’-DDT ratio was 0.48 (ranging 0.30-0.84). The high p,p’-

355

DDT/ p,p’-DDE ratios at some sites indicate that the emissions of DDT at these sites are

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recent.44 Also, the ratio is higher at some urban sites in Chittagong compared to other

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contemporary studies in Asia45, 46 and Europe.27 The low o,p’-DDT/ p,p’-DDT ratios indicate

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that sources to DDT were technical DDT (ratio >1)47 usage which has

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been reported in other studies from Asia.45, 46, 48, 49 Together, these results support that there is

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recent use and/or emissions from stockpiles of DDT in the Chittagong area.

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For the sum of HCHs, the median contribution from each isomer was 42%, 4%, and 54% for

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α-, β-, and γ-HCH, respectively. Similar contributions of both α- and γ- HCH to the sum HCH

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implies emissions of both technical HCH (α-HCH: 55-80%; β-HCH: 5-14%; γ-HCH 8-15%)

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and lindane (>90% γ-HCH).50 There were considerable amounts of γ-HCH found at the same

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sites that also contained the extremes for PCBs, PAHs and HCBs at the sites near ship 17 ACS Paragon Plus Environment


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breaking activities. This could indicate their common release and/or signatures of continued

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or historic use of lindane at that site.

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Sources of SCCPs

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The spatial pattern of SCCPs shows elevated concentrations in the city (Figure 1F). This

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suggests that the main emission sources may be located within the urban areas. SCCPs are

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known to be found in metal-working lubricants, sealants, plasticizers, and flame retardants.21

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It is plausible that these usages may represent potential sources in Chittagong as well. SCCPs

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were in the same orders of magnitude as the PAHs, which shows that these compounds are

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abundant in air in the Chittagong area.

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376

Human health risk assessment

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TEQ values based on PAHs and PCB-118 (ranging 0.39-40 ng TEQ/m3; SI, Table S5) were

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largely dominated by PAHs and above the carcinogenic risk limit (TEQ of >1 ng TEQ/m3)51

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at 18 of the sites. This indicates that PAH exposure through inhalation cannot be considered

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safe at several sites and could involve elevated health risks. The highest value for TEQ was

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found at the site with the highest concentrations in the ship breaking area (SI, Figure S5). It

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should be noted that the calculations: i) were based on a limited number of PAHs and only

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one PCB; and ii), incorporate the uncertainties of the PUF-derived concentrations in air. Still,

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the relatively large exceedance of the threshold found at some sites indicate that further

385

studies should address the health risks for humans in the areas with the highest concentrations

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of contaminants, with special consideration for the workers involved in the ship breaking

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activities. Possible exceedance of international standards and guideline values for health

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related to concentrations of SO2 and NO2 in ambient air has also been reported in this area.29

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The highest values in this study is higher than those reported in southern India where PAH18 ACS Paragon Plus Environment

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TEQs only exceeded the TEQ threshold in the summer months.41 As this study was performed

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in the season during the most intense industrial activities, levels of PAHs and PCBs could be

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lower during the wet season which also has less intense industrial activity. A follow-up study

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should therefore be performed to assess the seasonal variability of POPs in ambient air in

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Chittagong.

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Ship breaking activities in Bangladesh employ over 100,000 workers and an estimated 50,000

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children are involved in informal e-waste recycling of which 40% takes place in ship breaking

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yards.5 Detrimental health effects have been emphasized following occupational exposure

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related to informal recycling processes of obsolete ships12, 52, 53 and e-waste.54-56 There are

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considerable health hazards for workers within ship breaking that are related to accidents in

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addition to the chemical exposures from asbestos, heavy metals and POPs.12, 57 Furthermore,

401

significant correlations between concentrations of various POPs in air (including, PCBs,

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pesticides and PBDEs) and human serum have been reported in China which emphasizes the

403

relevance also of inhalation as exposure pathway in areas with considerable pollution.58 Thus,

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the concentrations of POPs in ambient air in Chittagong could be detrimental to human health

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and add to the health hazards related to ship breaking activities.

406

407

Comparisons with other studies

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Among the PAHs included in this study, phenanthrene was the most prevalent compound.

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This has also previously been observed in studies of background air performed in both Asia

410

(India and South Korea),41, 59 and Europe.27 However, the estimated median and maximum

411

concentrations of phenanthrene in this study were up to orders of magnitude higher than in the

412

studies referred to above. Furthermore, the concentrations of phenanthrene in this study was

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also higher than those in ambient air in Shanghai, China,60 and at industrial sites in Taiwan.61 19 ACS Paragon Plus Environment


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The estimated concentrations of Σ7PCBs in air at sites close to ship breaking activities were

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within the range of other contemporary monitoring results in Southeast Asian areas influenced

416

by informal e-waste treatment17, 62 or where e-waste treatment has been suggested to

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contribute to high concentrations63, 64 (Figure 3). The median concentration of Σ7PCBs in air

418

in Chittagong was comparable to those in large Asian cities45, 62, 64, 65 but higher than

419

European background sites.27 The PCB congener profile in air in Chittagong displayed less

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PCB-28 relative to the higher chlorinated congeners compared to that observed in multi-site

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studies in India and China49, 66 but was similar to that reported in multi-site studies in

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Europe.23, 27 In comparison to atmospheric PCB profiles resulting from industrial thermal

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processes, the observed contributions from PCB-28 were low, and can be considered similar

424

to those for secondary copper or zinc smelting.20 This result could be in agreement with the

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ship breaking and metal re-rolling activities in the area.

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The current concentrations of DDT are within the ranges of those found in ambient air in

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India.49 DDT is still actively used in India, which adds further support to the hypothesis of

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ongoing use of DDT in Chittagong. The concentrations of DDT were in the high range

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compared to other studies in China, Japan, South Korea and Europe.27, 48

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Concentrations of HCB in Chittagong were also in the high range in comparison to

431

concentrations found in the same studies mentioned above.27, 48

432

Estimations of sampling volumes are not presented for SCCPs by Harner et al.,35 but

433

assuming a sampling rate of 4.2 m3/day67 for 8 days, the median concentration of SCCPs is 46

434

ng/m3 which is several fold higher than concentrations reported in India and Pakistan

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(sampled in 2006 and 2011, mean 8.11 ng/m3, ranging

High Concentrations of Organic Contaminants in ... - ACS Publications

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